Certain imidazoline alkanoic acid salts of certain detergent acids and process



United States Patent Hans S. Mannheinier, New York, N. Y.

No Drawing. Application November 21, 1956, Serial No. 623,526

13 Claims. (Cl. 260-3095) This invention relates to novel compositionsand to methods for producing them. In one of its more specific aspectsthe invention is directed to methods of making and to novel derivativesof metal salts of substituted quaternary hydroxy cycloimidinic acidmetal alcoholates, examples of which are disclosed in my U. S. Patent2,528,378 and which I shall hereafter refer to herein as cycloimidates.

Said cycloimidates have been found useful because they have highdetergent, foaming, wetting, emulgating, emulsifying, dispersingbacteriastatic, bacteriacidal, fungicidal, and deodorizingcharacteristics. They are highly water-soluble, stable in aqueoussolutions in the pH range of 1-14 and are not precipitated out ofsolution by the salts normally present in hard water. They arenonvesicant and non-toxic to human and animal life and may be introducedinto the blood stream without ill effects. They are surface activeagents and serve as excellent synthetic detergents, softeners and dyeassistants in the textile and related fields and especially in washingand cleansing of cotton fibers andtextiles. They may also be employed astherapeutic agents and are especially useful as germicides, fungicidesand antisepticides.

Said cycloimidates have the following general Formula I:

i in which R is the organic radical which if connected to a I whosehydrogens may be hydroxy substituted,'illustraerably an alkali metal andfor most purposes is sodium or potassium. A; The methods for producingsaid cycloimidates and illustrative examples of 'a number of specificcycloimidates are disclosed in said patent. 1

Prior to this invention, it was known that cationic surface activeagents and anionic surface active agents when together in aqueoussolution resulted in the production or formation of water insolublecompounds; and that adding an anionic surface active agent to an aqueoussolution of another anionic surfaceactive agent resulted ice Saidcycloimidates normally behave anionically in aqueous solutions having apH above 7, and consequently it was expected that said 'cycloimidateswhen in aqueous solution together with anionic surface agents would becombined physically only and that no other reaction would occurtherebetween. In the course of my experimentations, I have discoveredthat said cycloirnidates could be reacted with certain anionic surfaceactive agents at a pH above 7 to produce water-soluble reactionproducts. Not only did I make said discovery, but I further discoveredthat water solutions of such reaction products had viscosities greaterthan corresponding aqueous solutions of the cycloimidates and alsoexhibited better foaming characteristics than did said cycloimidates invery low dilutions under extreme water hardness conditions. Saidreaction products are non-toxic and non-irritating to the human skin.They have been found eminently useful as general utility detergents,such as for car washing, dish washing, clothes washing, etc. Saidcycloimidates when used as components of shampoos sometimes causedslight irritation or stinging of the eyes when such shampoos were usedand water solutions thereof accidentally reached the eyes. I havefurther discovered that the reaction products of this invention causedpractically no irritation or stinging of the eyes when so employed.

According to this invention, one or a combination of two or more of saidcycloimidates of the general structural Formula I are reacted with oneor a combination of two or more anionic surface active agents of thefollowing genera-l structural Formula II to provide novel, water-solublecompounds having the following general structural Formula Ill, andhaving high wetting, detergency and surface active properties andcapable of providing voluminous and stable foams in aqueous solutions,and which aqueous solutions are'substantially non-irritating to the skinand eyes of normal human beings.

wherein R3 is selected from the group consisting of aliphatic andaliphatic-aromatic hydrocarbon radicals of 6-18 carbon atoms, with thealiphatic-aromatic hydrocarbon radicals each having an aliphatic radicalof at leastf6 carbon atoms; R4 is selected from the group consisting of(21) aliphatic hydrocarbon groups of 1-12 carbonatoms, (b) hydroxysubstituted aliphatic hydroin a mere physical combinationof said agentsand that no reaction would occur between them.

groups, each of said groups having at least one ether linkage therein,and otherwise beingflhydroxy substituted hydrocarbon of 2-12 carbonatoms, ('e) aliphatic groups, each group containing --CONH-- andotherwise being hydrocarbon of 2 12 carbon atoms; X is a radicalselected from the group consisting of 'SO;: and -OSO3; and M is analkali metal or its equivalent and preferably sodium or potassium; andRand Rahave heretofore been defined under Formula I. It is to beunderstood that X as it appears in the foregoing Formulas II andlll andas it appears hereafter in the description, .the specific exam'plesyandclaims is either S03 or 0803 unless other 3 wise specified, and, in thespecific examples, S03 may be substituted 7 for. C503 and Vl.CBr V6I'Sa,for i theyarelequivalents.

Said novel reaction products, compounds of Formula III are substantiallynon-irritating and do not cause stinging of the eyes while compounds ofFormula I as well as those of Formula ILeither alone or togethersometimes are irritatingand always cause stingingofzthe eyes.

According to this invention, I react a compound of Formula I with acompound ofFormula II to provide the novel and highly useful compoundsof Formula III. In general this reaction is carried out in a solutioncontaining compounds I and II and to which a quantity of an acidic agentsuch as a strong mineral acid, as for example hydrochloric, sulphuric orits equivalent, has been added to lower the pH of the solution to avalue of approximately 7 to approximately 9 and while maintaining themass at .a temperature between approximately 100200'F. In this reactionunder the aforesaid conditions, the quaternary hydroxy of-the compoundof Formula I combines with the metal of the compound of Formula II toproduce the metal hydroxy and the metal of the OM group of the compoundof Formula I is replaced by hydrogen due to the acidic'agent additionwhich also at least in part reacts with the formed metal hydroxycompound to form a water-soluble salt. The resultant solution can beused directly as a surface active agent, wetting agent or detergent forthe purposes indicated for the cycloimidates. While the quantities ofthe compound of Formula I and compound of Formula II may beequimolecular for good yield of compounds of Formula III, I may employan excess of either, and in general the mole ratio of a compound ofFormula I to compound of Formula Il may be 2 moles of the former to 1-3moles of the latter.

One of the specific methods which I prefer to employ in carrying out anaspect of this invention is to first dissolve a compound of Formula I inwater .and thenrthe pH thereof is adjusted to approximately 12-13(measured electrically) by the addition of aqueous caustic soda ifrequired so that when a compound of Formula II is added thereto, the pHof the solution of I and II will be at least and generally 105-11. Thetemperature of said solution is raised to HID-200 F. and preferably infactory practice to approximately 140 P. Then a quantity of acompound ofFormula II is dissolved in water in a separate container and thissolution is added to said first solution and the mass is maintained insaid temperature range while being constantly stirred, and an acidicagent is added thereto to reduce the pH thereof to a value below 10 andin the range of approximately 7 to 9, and preferably of approximately8.2 to approximately 8.7. At the end of by way of limitation, all parts.being given by weight 7 unless otherwise specified.

Example 1 .An aqueous solution of v400 parts of the lauric.cycloimidates,. of Example 1 of my heretofore identified patent, in 600parts of water is heated to approximately 140 'F. and its pH (measuredelectrically): is adjusted by the addition of aqueous causticsoda to12-13 ,While being constantly stirred and maintained at that.temperature there is added a solution of 350 parts ofC11H2s-COO-C2H4..S O3-'Na V in 600 parts of water. Then while stirringand the temperature is maintained there is slowly added theretohydrochloricacid-solution (32%) until the pH ofthe mass is lowered to avaluein the range of 8.2 to 8.7. Stirring is continued and thetemperature maintained for about 10 minutes more. The resultant productis a solution ,of (the novel reaction product having the following g formula:

/Og2 N om CzH|OH Employ the same procedure and components as set forthin Example 1,-exoept;-that only about parts of C11H23 COOC2H4'SOsN a areused. In this instance, the resultant product is a solution of thereaction product whose structural formulais shown in Example 1 togetherwith unreacted lauric .cycloimidate" ,used.

Employ the same procedure as that set forth in 'Example l, butemploy thecomponents indicated in the oll win Examples 3-11; the quantity ofhydrochloric acid solution (32%) is variable to lower the pH to valuesindicated in Example l'to obtain the reaction products of said vExamples3-11.

Example 3 400 parts of lauroyl cycloimidate (same as Example 1) in 600parts of water. 310 parts of V -CaHr1-COO-CH2(CHOH)CI-IzS0sNa in 600parts of water.

rnoltmurla on REACTION PRODUCT CHE-OOON CaH11-OOOCHz(CHOH).OH2-S0zExample 3-A Same procedureas,that of Example 3 except that the sodium.sulfatesaltiis used in place of the sulfcnate salt of Example 3 toprovide novel reaction product whose formula is exactly the same as thatof the novel reaction product of Example 3 except that 0803 issubstituted for the SQs therein. i

Example .4 3 50 parts pf lcaproyl cycloimidate of Example 3 of myhereinbeforeidentifiedpatent in 650 parts of water. 330; parts of aOHQOH QnHar-G 0 OC;F[aC-,OH20SOa-Na I i V VHEOH in 500 parts of water.uIlQRhIU LA.OF.NQYEL REACTION PRODUCT N/V \OH2 I C2H4-OH C lin-", i N/orn-oH out-000m cuawo qaiib=eu=.o t I V I Ii -1 v Example 5 V w FORMULAOF REACTION PRODUCE 4 00 parts of lauroyl cycloimidate (same asExample 1) in 600 parts of water.' 360 parts of N \CH:

C9H 19-C OO-C:H4OC2H4OSOa-Na 5 a l l arm-0H in 600 parts of water 011E?-N FORMULA 0:3 REACTION PRODUCT l CH2-COON3 o, V ClflHu-C C0O- BHr-O 0aN Example 10 t. v OaHr-OH' 1 1 400 parts of lauroyl cyclotmrdate (sameas Example P 1) in 600 parts of water. 420 parts of I CHs-OOONamm-ooo-mmomm-osm v C0111 C000:H4O S (h-N8 Example 6 400 parts of lauroylcycloimidate (same as Example 1) in 600 parts of water. 400 parts of 2111 600 Parts Of Watera C11Hzs COO C2H4CHOHOCI-IzOSO3--Na 0 FORMULA 0FREACTION PRODUCT a in 600 parts of water.

FORMULA 0F REACTION PRODUCT N t V O2H4 0H O r 011E l-N N CH: 23- II IOIHPOH I cur-000m CuHrs C 0 0-0 9Ht-0 S 08 OHz-OOONa 80CnHza-COO-CQHrCHOHO om-oso. pl 11 Example 7 400 parts of lauroylcycloimidate (same as Example 600 parts of stearoyl cycloimidate ofExample 6 of V 1) m 600 parts of water- 380 parts of my hereinbeforeidentified patent dissolved in 900 parts C11H23 COOCH2(CHOH)CH2 OSO3 N3of water. 500 parts of i 700 parts of water.

CmH21-COQ CH4NHCOCHz-SO3- -Na FORMULA 0F REACTION PRODUCT 'dissolved in750 parts of water. V

. CH2 FORMULA 0B REACTION PRODUCT N/ OH:

OH: (ll l/CsH4OH N/ \QH, I OHHSS -N p o,mo1=.r J om-ooom ,3 5,;onHaooo-oH=(cHoH)cHzo Os CHr-OOONa 'Ihe specific cycloimidates used inExamples 1-1l t herein may be replaced by any of the other specific cy-H Quin O00 CIHNHOOCHVSOQ cloinndates of my herembefore adentrfiedpatent, such 1-" a r 7 Example 8 as those of Examples 2, 4, 5, 7, 10-14therein; and in 450 parts of myrist 0Y1 cydoimidate of Example 8addition the spec1fic reactants I may diflier from those of myhereinbefore identified patent dissolved in 700 parts 5: 15gg figgi g ii i ifii 1 353? 311 13 553; of water. 500 parts of 5- cases being atleast 4 carbon atoms and preferably 4-18 C H COO;;C2H OC H 0C H OSO Ncarbon atoms, and also other hydrocarbon radicals Rs and groups R; thanthose specifically used herein may dissolved 750 parts of Water. also beemployed to provide a great variety of specific compounds illustratingthe present invention, also $03 P REACTION PRODUCT may be substitutedfor 0803 and vice-versa.

., E, It is to be understood that instead of first adjusting I N 0H, thepH of the cycloimidate to 12-l3 before the addia 7 tion of the compoundof Formula II, any other method 1 i i 2 a :1 may be employed to obtainthe condition whereby the f Cm-f-OQ'ON erably 10.5-11 before theaddition of the acidic agent I r to lower the pH of the mass toapproximately 7 to apf ii 9.?9 9E1. 9 7 proximately 9. For example, Iand II may be dissolved a 7 together and this solution may bytheaddition of caustic r 11* soda when required have its pH adjusted toat least 10, 400 parts of lauroyl -CyCl01Illldat6? (same as Example andthan at 1004000 B is readyifory the addition of they 1) intsoo parts ofa s-9 acidic agent to lower its pH to approximately 7 to apl l.proximately 9. (Mm-@709OOZHPOSOPNa Sin'cecertain changes in carrying outthe aforesaid processesand certain modifications in the compositions in650 parts of water. r which embody the invention may be made withouttie-' Examp 65 pH of the solution of I and II is at least 10 and pref- 7parting from its scope, :it is in't'en'ded that all matter contained inthe description shall be interpreted as illustrative and not ip alimiting sense.

It is also to be understood that the following claims are intended "tocover all the generic and specific features of the invention hereindescribed, and all statements of the scope of theinv'enti-on which as amatter of language migh-t'be said tofall therebetween.

This application is 'a continuation-impart of --mly copendingapplication 565,538 filed February 15, 1956, now abandoned, which inturn is acontinuation-in-part of my application, Serial No. 481,703,filed January 13, 1955, and since abandoned.

Iclaim:

1. A novel compound of the following formula:

in which R is a hydrocarbon radical of 4-18 carbon atoms; R2 is anorganic group selected from :the class consisting of (a) aliphatichydrocarbon groups of 1-4 carbon atoms, (b) hydroxy substitutedaliphatic hydrocarbon groups of 1-4 carbon atoms, (c) aliphatic ethergroups, each of said groups having a single ether linkage therein andotherwise being hydrocarbon of 2-4 carbon atoms, (a!) aliphatic ethergroups, each of said groups having a single ether linkage therein andotherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms, (e)aliphatic keto groups, each of said groups having a single keto linkagetherein and otherwise being hydrocarbon of 2-4 carbon atoms, aliphaticketo groups, each of said groups having a single keto linkage thereinand otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms;R3 is selected from the group consisting of aliphatic andaliphatic-aromatic hydrocarbon radicals, with said aliphatic radicalscontaining 6-18 carbon atoms, and said aliphatic-aromatic radicalsselected from the class of benzene and naphthalene rings, each having analiphatic radical of 6-18 carbon atoms attached thereto; R4 is anorganic group selected from the-class consi'sting of (g) aliphatichydrocarbon groups of 1-12 carbon atoms, (12) hydroxy substitutedaliphatic hydrocarbon groups of 1-12 car-bon atoms, (i) aliphatic ethergroups, each of said groupshaving at least one ether linkage therein andotherwise being hydrocarbon of Z-IZ carbon atoms (j) hydroxy substitutedether groups, each of said groups having at least one ether linkagetherein and otherwise being hydroxy substitutedhydrocarbon of 2-12carbon atoms, (k) aliphatic groups, each of said groups containing CONHand otherwisebeinghydrocar} bon of 2-12 carbon atoms; X is selectedfromthegfoup consisting of S03 and 050s; and M is an alkali metal;

2. A novel compound of the following formula:

. i N/ 7 OH:

n I elm-on R-d-N oHr-ooo-Na m-o o o-crmoz 3. A novel compound of'th'e tollowing formula:

- f om- R --N a Marases Ra-COO-CHKCH'Ci-DCHz-SO:

in which R is a hydrocarbon radical of 4-18 carbon atoms and R3 isanaliphatic hydrocarbon radical of 6-18 carbon atoms. I u j 4. A novelcompound of the following formula:

in which R is a hydrocarbon radical of 4-18 carbon atoms and R3 is analiphatic hydrocarbon radical of 6-18 carbon atoms.

5. A novel-compound of the following formula:

P's-o0 'o-oraro crui-osos in which R is a hydrocarbon radical of 4 -l 8carbon atoms and R3 is an aliphatic hydrocarbon radical of 6-18 carbonatoms. a V

6. A novel compound of the tollowingforrnula:

7. .A novel compound of the following formula:

8. The method for the preparation of a compound defined in claim 1',comprising under pH conditions of ap- 5 proximately 7 to approximately 9reacting with each other compounds of the following Formulas I and II:

in which R is a hydrocarbon radical of 4-18 carbon atoms; R2 is anorganic group selected from the class consisting of (a) aliphatichydrocarbon groups of 1-4 carbon atoms, (b) hydroxy substitutedaliphatic hydrocarbon groups of 1-4 carbon atoms, aliphatic ethergroups, each of said groups having a single ether linkage therein andotherwise being hydrocarbon of 2-4 carbon atoms, (a') aliphatic ethergroups, each of said groups having a single ether linkage therein andotherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms, (e)aliphatic keto groups, each of said groups having a single keto linkagetherein and otherwise being hydrocarbon of 2-4 carbon atoms, (7)aliphatic keto groups, each of said groups having a single keto linkagetherein and otherwise being hydroxy substituted hydrocarbon of 2-4carbon atoms; R: is selected from the group consisting of aliphatic andaliphatic-aromatic hydrocarbon radicals, with said aliphatic radicalscontaining 6-18 carbon atoms, and said aliphatic-aromatic radicalsselected from the class of benzene and naphthalene rings, each having analiphatic radical of 6-18 carbon atoms attached thereto; R4 is anorganic group selected from the class consisting of (g) aliphatichydrocarbon groups of 1-12 carbon atoms, (h) hydroxy substitutedaliphatic hydrocarbon groups of 1-12 carbon atoms (i), aliphatic ethergroups, each of said groups having at least one 10 carbon of 2-12 carbonatoms, (k) aliphatic groups, each of said groups containing CONH andotherwise being hydrocarbon of 2-12 carbon atoms; X is selected from thegroup consisting of S03 and OSOs; and M is an alkali metal.

9. The method comprising to a solution containing a compound of FormulaI and a compound of Formula II both defined in claim 8, adding aquantity of an acidic agent to lower the pH thereof to a value ofapproximately 7 to approximately 9 and maintaining the temperature ofthe mass between about 100 F. and 200 F.

10. The method comprising to a solution whose pH is at least 10 andcontaining a compound of Formula I and a compound of Formula II bothdefined in claim 8, adding a quantity of an acidic agent to lower the pHthereof to a value of approximately 7 to approximately 9 and maintainingthe temperature of the mass between about 100 F. and 200 F.

11. The method defined in claim 8, with the mole ratio of compound ofFormula I to compound of Formula II being 2 moles of the former to 1-3moles of the latter.

12. The method defined in claim 10, with the mole ratio of compound ofFormula I to compound of Formula II being 2 moles of the former to 1-3moles of the latter.

13. The method defined in claim 10, with the mole ratio of compound ofFormula I to compound of Formula II being 2 moles of the former to 1-3moles of the ether linkage therein and otherwise being hydrocarbon oflatter.

2-12 carbon atoms, (j) hydroxy substituted ether groups,

each of said groups having at least one ether linkage therein andotherwise being hydroxy substituted hydro- No references cited.

1. A NOVEL COMPOUND OF THE FOLLOWING FORMULA: IN WHICH R IS AHYDROCARBON RADICAL OF 4-18 CARBON ATOMS; R2 IS AN ORGANIC GROUPSELECTED FROM THE CLASS CONSISTING OF (A) ALIPHATIC HYDROCARBON GROUPSOF 1-4 CARBON ATOMS, (B) HYDROXY SUBSTITUTED ALIPHATIC HYDROCARBONGROUPS OF 1-4 CARBON ATOMS, (C) ALIPHATIC ETHER GROUPS, EACH OF SAIDGROUP HAVING A SINGLE ETHER LINKAGE THEREIN AND OTHERWISE BEINGHYDROCARBON OF 2-4 CARBON ATOMS, (D) ALIPHATIC ETHER GROUPS EACH OF SAIDGROUPS HAVING A SINGLE ETHER LINKAGE THEREIN AND OTHERWISE BEING HYDROXYSUBSTITUTED HYDROCARBON OF 2-4 CARBON ATOMS, (E) ALIPHATIC KETO GROUPS,EACH OF SAID GROUPS HAVING A SINGLE KETO LINKAGE THEREIN AND OTHERWISEBEING HYDROCARBON OF 2-4 CARBON ATOMS, (F) ALIPHATIC KETO GROUPS, EACHOF SAID GROUPS HAVING A SINGLE KETO LINKAGE THEREIN AND OTHERWISE BEINGHYDROXY SUBSTITUTED HYDROCARBON OF 2-4 CARBON ATOMS, R3 IS SELECTED FROMTHE GROUP CONSISTING OF A LIPHATIC AND ALIPHATIC-AROMATIC HYDROCARBONRADICALS, WITH SAID ALIPHATIC RADICALS CONTAINING 6-18 CARBON ATOMS, ANDSAID ALIPHATIC-AROMATIC RADICALS SELECTED FROM THE CLASS OF BENZENE ANDNAPHTHALENE RINGS, EACH HAVING AN ALIPHATIC RADICAL OF 6-18 CARBON ATOMSATTACHE THERETO; R4 IS AN ORGANIC SELECTED FROM THE CLASS CONSISTING OF(G) ALIPHATIC HYDROCARBON GROUPS OF 1-12 CARBON ATOMS, (H) HYDROXYSUBSTITUTED ALIPHATIC HYDROCARBON GROUPS OF 1-12 CARBON ATOMS, (I)ALIPHATIC ETHER GROUPS, EACH OF SAID GROUP HAVING AT LEAST ONE ETHERLINKAGE THEREIN AND OTHERWISE BEING HYDROCARBON OF 2-12 CARBON ATOMS (J)HYDROXY SUBSTITUTED ETHER GROUPS, EACH OF SAID HAVING AT LEAST ONE ETHERLINKAGE THEREIN AND OTHERWISE BEING HYDROXY SUBSTITUTED HYDROCARBON OF2-12 CARBON ATOMS, (K) ALIPHATIC GROUPS, EACH OF SAID GROUPS CONSISTINGCONH AND OTHERWISE BEING HYDROCARBON OF 2-12 CARBON ATOMS; X IS SELECTEDFROM THE GROUP CONSISTING OF SO3 AND OSO3; AND M IS AN ALKALI METAL.